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LINwooD '1. RICHARDSON, or MILWAUKEE, WISCONSIN, AND ELWOOD A. RICHARDSON,

OF CLEVELAND, OHIO.

ALLOY.

To all whom it mag concern Be it known that we, LINWOOD T. RICH- ARDSON, a citizen of the United States, and ELwoon A. RICHARDSON, a citizen of the United States, residing, respectively, at Milwaukee, county of Milwaukee, State of \Visconsin, and at Cleveland, county of Guyahoga, State of Ohio, have invented certain new and useful Improvements in Alloys; and we do hereby declare the following to be a full, clear, and exact description of the invention, such as will enable others skilled in the art to which it appertains to make and use the same.

Our invention relates to ferrous alloys, and has for its general object the production of an improved rust or corrosion-resisting ferrous alloy.

Iron, in any of its well known commercial forms, oxidizes or rusts more or less easily When exposed to the atn'iosphere. \Vhile many expedients and agencies have heretofore been employed or suggested for preventing or minimizing this natural tendency of iron to oxidize, as far as we know, the beneficial effects of certain metallic substances in preventing or minimizing the natural tendency of iron in its usual commercial forms to rust have not been recognized. e have discovered that certain metals exercise in combination a very beneficial effect in minimizing the rusting or corrosion of iron when these metals are present therein in certain predetern'iined quantities. Thus, we have found that copper and manganese, when added in certain percentages to iron, produce a ferrous alloy having rustresisting characteristics which are not possessed by iron without such additions of copper and manganese. The corrosion of the iron is lessened by the addition of either copper or manganese,,but we have discovered that the two metals acting together produce an effect greater than either alone. And we have further found that the manganese may be in whole or in part replaced by chromium in which event the combined effect of the copper and chromium, or copper, manganese and chromium, is to minimize and materlally reduce the natural tendency of the iron to rust, as compared with iron in which such modifying agents are not present Within the percentages contemplated by our present 1nvention.

Specification of Letters Patent.

Patented Sept. 30, 1919.

Application filed June 3, 1918. Serial No. 237,904.

The present invention involves the addition to or alloying wlth 1ron, 1n any of its usual. commercial forms, of certain relatively small quantities of two or more metallic modifying agents, whose combined effect upon the iron is to increase or improve its rust-resisting properties. The beneficial efl'ect resulting from the addition of two or more such modifying agents to iron is due to the combined action of the agents. Thus, while any one agent acting alone might improve the rust-resisting properties of iron, we have found that the combined action of two or more of the modifying agents produces a more pronounced improvement in the rust-resisting properties of iron than does any one agent when used alone.

The metallic modifying agents which We add to iron to improve or ameliorate its rustresisting properties by their combined action may be divided into two classes, to Wit, a. major modifying agent and a minor modifying agent or agents. The major modifying agent is that which if alone added to the iron would produce the most marked improvement in the rust-resistin properties thereof, while the minor modi ying agents are those which if alone added to the iron would produce some improvement in the rust resisting properties thereof, but not as great an improvement as the major modifying agent acting alone. And further, in accordance with the rinciples of our present invention, the ma or modifying agent in combination with one or more minor modition, We use in comblnation with copper, one' or more minor modifying agents whose com bined effect with copper is to produce a greater improvement in the rust-resisting properties of the iron than is produced by copper alone, or by any one of the minor modifying agents alone. ,.As such minor modifying agents we prefer to use either manganese or chromium, or manganese and chromium.

We have determined, in using copper alone as the modifying agent for improving the rust-resisting properties of iron, that little advantage results in using more than about 2.0% of copper, and for most practical purposes the most satisfactory results are obtained by using from 1.5% to 2% of copper. With manganese alone, we have found that the decrease in corrosion or rusting of the iron is little marked up to about 2% of manganese. There is, however, little practical advantage in using a greater percent age of manganese, because ferrous alloys containing more than about 2% of manganese are brittle and hard to work, as will be more fully explained hereinafter.

In accordance with the principles of our present invention, the copper and manganese operate together to produce a more pronounced improvement in the rust-resist ing properties of iron than would either metal if alone alloyed with iron. We have determined that little improvement in its rust-resisting properties results from the addition of copper to aferrous alloy containing more than about 1% of manganese, or from the addition of more than 2% of cop per to a ferrous alloy of any manganese content. In general, we prefer to alloy with the iron from about 1.0% to about 2% of copper and about 1% of manganese.

As we have. hereinbefore mentioned, the manganese may be in whole or in part replaced by chromium. Generally speaking, we have found it advisable to employ, in combination with copper, a slightly larger percentage of chromium than mentioned in the case of manganese. Thus, in using chro- Inium alone, as the minor modifying agent, we prefer to employ from about 1.5% to about 2% thereof. When both manganese and chromium are to be used in combination with from about 1% to about 2% of copper, we have found a combined manganese-chromium content of from about 1%- to about 2% to give satisfactory results.

In the preceding paragraphs We have mentioned specific percentages which we have found to produce the most satisfactory results in improving the rust-resisting properties of ferrous alloys. We wish it to be understood, however, that we do not intend thereby to limit our invention to the employment of such specific percentages of the modifying agents, since our mvention in its broad aspect is capable of advantageous application without particular reference to the specific percentages mentioned. In its broader aspect our invention thus contemplates the use of from about 1.5% to about 4% of a plurality of combined metallic modifying agents, each of which is present in quantitiesfrom about 0.5% to about 2%. The balance of the ferrous alloy is composed principally of iron. And, of course, it will be understood that the modifying agents are of such a character that they produce in combination a more pronounced improvement in the rust-resisting properties of the resulting ferrous alloy than would be produced by using any one of the modifying agents alone.

Alloys of iron and copper alone do not forge satisfactorily. When red hot such al-' loys are brittle and smash when struck with a hammer. At low temperatures they can be forged by using extreme care, and by expending a great deal of energy. There appears to be a range of temperatures at which any particular copper-iron alloy cannot be satisfactorily worked or forged at red heat. With increasing copper content this redshort or non-malleable temperature range occurs at a lower temperature and exists over a longer interval. For example, in the case of one series of copper-iron alloys which we tested, we found that the iron with zero per cent. copper could be forged at all tem-' peratures, with 0.25% copper the resulting ferrous alloy could not be forged between 940-1010 0., and with 0.5% copper the alloy could not be forged between 890950 (1., while with 0.75% cop-per the alloy could not be forged between 8-50910 C. This red-shortness, or non-forgeabili-ty at red heats, of copper-iron alloys means that these alloys cannot be satisfactorily worked or forged in a hot state. The presence of manganese or chromium in such quantity as we contemplate for improving the rust-resisting properties of iron, eiiminates this non-forging temperature range, so that the manganese- (or chromium) copper-iron alloy can be worked at all temperatures. The manganese or chromium, therefore, has the further function of rendering the ferrous alloy malleable as well as of increasing its resistance to atmospheric corrosion, which function is of great importance in the practical use of the alloy.

While we have thus found that manganese of chromium' added to a copper-iron alloy besides reducing the corrodibility,-also enables the alloy to be forged Without breaking,-We have further determined that the forging of the alloy becomes more difficult if themanganese or chromium cpntent exceeds about 2%. Thus, copper-iron alloys containing over 2% of manganese or chromi-. um are quite hard when hot and while such alloys can be forged without breaking much manganese or chromium content of less than 2% the alloy files and grinds easily and bends readily. With a manganese content greater than 2%, the alloy is difficult togrind, is almost impossible to scratch w th an ordinary file, and is quite brittle, while with a chromium content above about 2%, the alloy becomes tough and harder to work. These properties, within the range of copper content contemplated by the present invention, appear to be a function of the manganese or chromium content and to be independent of the copper. For these reasons we deem it advisable in the practice of our prment invention, to use less than 2% of manganese or chromium, in combination with copper, for improving the rust-resisting properties of iron.

lVhile our present invention is applicable in principle to iron in any of its well known commercial forms, it is particularly applicable to steel and ingot iron because of the ease with which the metallic modifying agents can be added thereto. Thus, the-copper may be introduced by using pig or cast iron containing the necessary percentage of this metal, or pure copper or a suitable alloy of copper may be added to the molten iron, either in the furnace, in the ladle, or in the molten ingot. The manganese may be added in the furnace or in the ladle as such or in the form of an alloy, such, for example, as ferro-manganese. Chromium may be introduced in substantially the same way as manganese or by using a pig iron containing it. Further, steel scrap containing one or all of the metallic modifying agents may be used. The essential thing in any case is to get the modifying agents into the iron so that they are uniformly distributed.

The matter of costs is of considerable importance in the case of iron or steel for or.- dinary commercial uses. It is, therefore, im-

portant to keep the cost of our improved rust-resisting ferrous alloy as near as possible to the cost of ordinary iron or steel of a corresponding grade. The increased cost of our improved product above ordinary iron or steel of the same grade is due to the required additions of the metallic modifying agents. As far as possible, therefore, weprefer to use scrap products for the introduction of such additional quantities of the modifying agents as .our'invention contemplates, and also, where possible, to use materials in the production of the crude or unmodified iron or steel product which contain one or more of the modifying agents in quantities of value in the carrying out of our invention.

Thus, instead of adding copper to the crude iron or steel, it is possible to use an iron ore containing copper, in which case the copper enters'the iron. or steel in the pig iron obtained in the blast furnace operation. The use of copper-bearing ores prob-' ably would not furnish all of the required amount of copper, so that additional amounts would have to be added to the molten iron. Such additions of copper may be obtained from scrap products containing copper, such, for example, as turnings of German silver, Monel metal and th like. Where such copper alloys are employed it will be. evident that metals other than copper may be introduced into the iron, but the quantities in which such other metals are present in the resulting ferrous alloy are relatively small and do not interfere with the effect of the copper or appreciably alter the properties of the ferrous alloy.

In the smelting of iron ore for the production of pig iron, which later by remelting is changed to cast iron, or by remelting and refining becomes wrought iron, ingot iron or steel, certain impurities in the ore itself, the coke and the slag, alloy with the iron. The most common of these impurities are carbon, phosphorus, sulfur, silicon and manganese, since these always occur in the raw materials. In certain iron ores other elements exist and these also appear in the pig iron, such as copper, nickel, chromium and titanium. At the present time, manganese is almost universally used as a deoxidizer of iron, and hence practically all commercial steels contain this element. In the refining process some of the impurities are oxidized in preference to the iron and are removed, while with others, the iron is more readily oxidized and hence these latter are not removed but appear in the final product. To the former class belong carbon, silicon, phosphorus, sulfur, and manganese, while to the latter class belong copper and nickel. Chromium may be eliminated or not, as desired, depending upon the method used in refining. It may be said then that commercial irons and steels are in an unstable state as regards corrosion and by the application of our present invention a great improvement can be effected in their rust-resisting properties by small changes in the copper-manganese or copper-chromium, or copper-manganesechromium content thereo'f. 7

Thus, by using ores, containing one or more of the metallic modifying agents contemplated by our present invention, the cost of making the additions of these agents to the iron is much reduced. Iron ores containing copper, nickel and chromium, or chromium and nickel, may accordingly be advantageously used in the production of our improved rust-resisting ferrous alloy. Take, for example, an iron ore containing 1 to 2% of chromium and 1% of nickel. In the smelting and refining of such an ore the nickel will appear in the iron while the chromium will or will not, depending upon the process used. Here then, there exists a raw material, in the shape of the ore, which when used will give an alloy containing chromium and nickel to which copper must be added to produce a rust-resisting iron, and to which manganese will probably have to be added as a deoxidizer. This leads to a rather complex ferrous alloy containing chromium, manganese, copper and nickel. The nickel is not added intentionally but gets into the final product since it exists in the ore. It will, therefore, be seen that our improved rust-resisting ferrous alloy may contain other metals besides the particular modifying elements which we have found to exercise, in combination, such a beneficial effect upon the rust-resisting properties of iron. Such other metals are not intentionally introduced, but their presence is due to the raw materials used in carrying out our invention. Although we prefer to use manganese or chromium, or both, as the minor modifying agent, any metal exercising in combination with copper the same effect in improving the rust-resisting properties of iron may be used if desired. Thus tungsten, molybdenum, titanium and aluminum might be used instead of manganese or chromium, and in the appended claims we have designated the minor modifying agents contemplated in the practice of the present invention as malleabilizing agents with respect to the influence of the copper on the malleability of the ferrous alloy, since, as previously explained, the minor modifying agents serve to render malleable the ferrous alloy which would be otherwise non-malleable as a result of the copper present. It will, of course, be understood that by ferrous alloy we mean. an alloy containing principally iron and generally speaking we may say that our improved ferrous alloy contains at least 90% of iron.

We claim:

1. The improvement in the art of producing corrosion-resisting ferrous alloys which comprises ameliorating the normal tendency to corrode of an article composed principally of iron by associating with the article in the form of an alloy with the iron a plurality of metallic modifying agents one of which is copper in excess of 0.5% and the other or others are malleabilizing agents with respect to the influence of the copper on the malleability of the ferrous alloy, the combined effect of said modifying agents in ameliorating the corrosion-resisting properties of iron being more pronounced than is the effect of any one of the modifying agents when used alone; substantially as described.

2. The improvement in the art of producing corrosion-resisting ferrous alloys which comprises ameliorating the normal tendency to corrode of an article composed principally of iron by associating with the article in the form of an alloy with the iron, a combined percentage of from about 1.5to about l'ofa plurality of metallic modifying agents I whose combined effect in improving the corrosion-resisting properties of iron is more" pronounced than is the effect of anyone of the modifying agents when used alone, one

of said agents being copper and the other or others of said agents being malleabili-zing' alloy; the amount of each agent present be-v ing from about 0.5% to 2% as described. 1

3. The improvement in the art of-producing corrosion-resisting ferrous alloys which comprises ameliorating the normaltendency to corrode of an article composed principally of iron by associating with the article in the form of an alloy with the iron a combined percentage of from about 1.5 to about at of copper and manganese, the copper and manganese being each present in an amount from about 0.5% t 2%; substantially as described.

4. The improvement in the art of producing corrosion resisting ferrous alloys substantially which comprises ameliorating the normal scribed.

5. As a new artlcle of manufacture, a corrosion-resistmg ferrous alloy composed principally of iron and in which the normal tendency of the iron to corrode is ameliorated by the combined influence of from about 0.5% to about 2% of copper and from about- 0.5% to about 2% of manganese associated in the form of an alloy with iron; substantially as described.

6. As a new article of manufacture, a corrosion resisting ferrous alloy composed principally of iron and in which the normal tendenc of the iron to corrode is ameliorated by t e combined influence of such a percentage of copper as to render the ferrous alloy when hot substantially non-malleable if alone contained therein and-another metal {whose effect in combination with the copper is to render the ferrous alloy malleable, said two metals operating together to produce a more pronounced improvement in the corrosion-resisting properties of the ferrous alloy than would be produced by theme of either metal alone; substantially as described.

7. As a new article of'manufacture, acorrosion resisting ferrous alloy composed principally of iron and in which the normal tendency of. the iron to corrode is ameliorated by the combined influence of from about 1% to about 2% of copper and such a percentage of manganese as to render the resulting ferrous alloymalleable; substantially as described. Y 8. As a new article .of manufacture, acorrosion-resisting ferrous (alloy principally of iron and in whic the normal tendency of the iron to corrode is ameliorated by the combined influence of'such a percentage of copper asfto render'the ferrous allo when hot substantially non-malleable if a one contained therein andsuch aper- 'centage of manganese as to render the remanganese, substantially as described. A

10. As a new article of manufacture, a

corrosion-resisting ferrous alloy composed principally of iron and in which the normal tendency of-the iron to corrodeis ameliorated by the combined influence of from about 1%to 2% of copper. and about 1% of manganese; substantiall as described.

' 11. An article of manu acture which is subjected-to corrosive influences comprising a ferrous alloy composed principally of iron and .in which the normal tendency of the composed iron to corrode is ameliorated by the combined'influence of such apercentage of copper as to render the ferrous alloy when hot substantially non-malleable if alone contained therein, and another metal whose effect in combination with the copper is to render the ferrous alloy malleable, said two metals operating together to produce a more pronounced improvement in the corrosionresisting properties ofthe ferrous alloy than would be roduced by the use of either metal alone; su' stantially as described.

12. An article of manufacture which is subjected to corrosive influencescomprlsing a ferrous alloy composed rincipally of iron and ,in which the norma tendency of the v iron to corrode is ameliorated by the combined influence of from about 0.5% to about 2% of copper andfrom about 0.5% toabout 2% of manganese associated in the form of an alloy with the iron; substantially as d scribed.

13. An article of manufacture which is subjected to corrosive influences COIIlPI'lSlIlg a ferrous alloy'composed principally of iron and in.which the normal tendency of the iron to corrode is ameliorated by'thecombind influence of from aboutl% to about 2% of copper and about 1% of manganese; subst ntially as described.

In witness whereof, we aflix our signatures. 4

,LINWOOD T. RICHARDSON. ELWOOD A. RICHARDSON. 

